US8729256B2 - Isomerization of sugars - Google Patents
Isomerization of sugars Download PDFInfo
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- US8729256B2 US8729256B2 US13/007,389 US201113007389A US8729256B2 US 8729256 B2 US8729256 B2 US 8729256B2 US 201113007389 A US201113007389 A US 201113007389A US 8729256 B2 US8729256 B2 US 8729256B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
Definitions
- the disclosed invention is in the field of isomerization of sugars.
- Carbohydrate-based chemical processes are of growing importance in view of the desire to use renewable feedstocks such as biomass.
- the isomerization of sugars is an important class of reactions used in various industrial carbohydrate-based processes.
- the conversion of glucose into fructose is one such process of particular significance.
- This reaction has been used for the production of high-fructose corn syrups (HFCS) as well as for the production of valuable chemical intermediates, such as 5-hydroxymethylfurfural (HMF) and levulinic acid.
- HFCS high-fructose corn syrups
- HMF 5-hydroxymethylfurfural
- Industrial glucose isomerization is generally accomplished using an immobilized enzyme, which offers the benefit of high conversion and selectivity, but also presents numerous challenges.
- the enzymatic catalysts do not maintain high activity over multiple cycles, cannot be easily regenerated, and do not perform over a wide variety of temperatures, pHs, salt concentrations, and other process conditions.
- enzymatic isomerization catalysts cannot be easily integrated into upstream processes for forming glucose from biomass, or into downstream processes for transforming fructose into other chemical intermediates.
- one preferred industrial isomerization method involves the use of an immobilized enzyme (xylose isomerase) at 333 K that generates an equilibrium mixture of 42% (wt/wt) fructose, 50% (wt/wt) glucose, and 8% (wt/wt) other saccharides.
- an immobilized enzyme xylose isomerase
- fructose yields are high, this enzymatic process has various drawbacks that include: (i) the need for various prereaction purification processes to remove impurities from the feed that strongly inhibit enzyme activity, e.g., calcium ions present from a previous starch liquefaction/saccharification step must be removed to levels ⁇ 1 ppm, (ii) the use of buffered solutions to maintain an optimal pH between 7.0 and 8.0 (Na 2 CO 3 ) and to activate the enzyme (MgSO 4 ) that requires postreaction ion-exchange procedures, (iii) an optimal operating temperature of 333 K to maximize both product yield and enzyme lifetime that precludes faster reaction rates that could be attained at more elevated temperatures, and (iv) higher operating costs resulting from the periodic replacement of the catalyst bed due to the irreversible decay in activity suffered by the enzyme over time.
- enzyme activity e.g., calcium ions present from a previous starch liquefaction/saccharification step must be removed to levels ⁇ 1
- processes are disclosed herein including processes for isomerizing a monosaccharide including contacting the monosaccharide in aqueous medium with a high-silica zeolite containing tin or titanium, incorporated into the framework of the zeolite, the zeolite having pores capable of admitting the monosaccharide.
- Processes are also disclosed for isomerizing a monosaccharide including contacting the monosaccharide in aqueous medium with an ordered mesoporous silica material containing tin or titanium, incorporated into the framework of the material.
- Further processes are also disclosed for converting glucose to 5-hydroxymethylfurfural including contacting glucose in aqueous medium with a high silica zeolite containing tin or titanium, incorporated into the framework of the zeolite, the zeolite having pores capable of admitting the glucose, to provide fructose; and dehydrating the fructose.
- Still further processes are disclosed for converting starch to 5-hydroxymethylfurfural including hydrolyzing the starch in acid to provide glucose in an acidic aqueous medium; contacting glucose in aqueous medium with a high silica zeolite containing tin or titanium, incorporated into the framework of the zeolite, the zeolite having pores capable of admitting the glucose, to provide fructose; and dehydrating the fructose.
- FIGS. 1-3 depict the structures and pore sizes of several different materials synthesized and tested for sugar isomerization activity.
- FIGS. 4-5 depict a zeolite structure containing titanium in the framework.
- FIG. 6 depicts a scanning electron microscope image of tin zeolite beta.
- FIG. 7 depicts a scanning electron microscope image of tin zeolite beta.
- FIGS. 8-11 depict scanning electron microscope images of titanium zeolite beta ( FIGS. 8-9 ) and tin zeolite beta ( FIGS. 10-11 ).
- FIG. 12 depicts ultraviolet/visible diffuse reflectance spectra of Sn-Beta and Ti-Beta.
- FIG. 13 depicts X-ray powder diffraction patterns of Ti-Beta and Sn-Beta.
- FIGS. 14-15 depict the absence of significant morphological changes of Sn-Beta using scanning electron microscopy after the conversion of glucose to HMF in a biphasic system.
- FIG. 14 depicts Sn-Beta before the reaction
- FIG. 15 depicts Sn-Beta after exposing Sn-Beta to glucose at a molar ratio of 200, 1:3 water to THF volume ratio, pH of 1 in HCl, 35 g of NaCl in 100 g of water.
- FIG. 16 depicts a schematic representation of the glucose isomerization reaction pathways catalyzed by either biological or chemical catalysts.
- FIG. 17 depicts a schematic representation of the glucose isomerization mechanisms by way of (A) base-catalyzed and (B) metal-catalyzed reaction pathways.
- FIG. 18 depicts a schematic representation of the glucose isomerization mechanisms by way of (A) proton transfer and (B) intramolecular hydride shift.
- FIG. 19 depicts the Meerwein-Ponndorf-Verley (MPV) reaction pathway.
- R alkyl or aryl;
- R1 and R3 alkyl or hydrogen;
- Me metal.
- FIG. 20 depicts a schematic representation of the pathway from biomass to glucose to HMF to fructose to downstream products.
- FIG. 21 depicts a schematic representation of the pathway from starch to glucose to fructose to HMF.
- FIG. 22 depicts a schematic representation of the use of a biphasic system for the reaction of glucose to form fructose to form HMF.
- FIG. 23 depicts the results of a screening of metallosilicates for the glucose isomerization reaction.
- the reaction conditions were 10 wt % glucose in water, 140° C., 90 min, and 1:50 metal:glucose molar ratio.
- FIG. 24 depicts the results of the glucose isomerization reaction catalyzed by various metal containing solids (Glucose conversion in stripes, Fructose selectivity in white). Reaction conditions were 10 wt % glucose in water, 413 K, 90 min, and 1:50 metal:glucose molar ratio.
- FIGS. 25-30 depict glucose isomerization reaction profiles and product distributions as a function of time at 363 K, 383 K, and 413 K for Glucose (stripes from lower left to upper right), Fructose (white), and Mannose (stripes from upper left to lower right) using Sn-Beta as a catalyst. Reaction conditions were 10 wt % glucose in water and 1:50 Sn:glucose molar ratio. The error bars for the reaction profile plots on FIGS. 25 , 27 , and 29 are not visible because they are smaller than the data-point icons.
- FIG. 31 depicts 13 C NMR spectra of a) unlabeled glucose, b) labeled glucose-D2, c) glucose fraction obtained after reacting glucose-D2 with Sn-Beta, d) glucose fraction obtained after reacting labeled glucose-D2 with NaOH, e) unlabeled fructose, 0 fructose fraction obtained after reacting labeled glucose-D2 with Sn-Beta, and g) fructose fraction obtained after reacting labeled glucose-D2 with NaOH.
- FIG. 32 depicts 1 H NMR spectra of a) unlabeled glucose, b) labeled glucose-D2, c) glucose fraction obtained after reacting glucose-D2 with Sn-Beta, d) glucose fraction obtained after reacting labeled glucose-D2 with NaOH, e) unlabeled fructose, f) fructose fraction obtained after reacting labeled glucose-D2 with Sn-Beta, and g) fructose fraction obtained after reacting labeled glucose-D2 with NaOH.
- FIG. 33 depicts (A) Glucose isomerization reaction and product distributions (glucose-stripes from lower left to upper right, fructose-white, and stripes from upper right to lower left) after 45 minutes at 383 K using Sn-Beta or SnO 2 -Beta. Reactions were performed with a 10 wt % glucose solution, using the corresponding amount of catalyst to maintain a 1:100 metal:glucose molar ratio; and (B) Diffuse reflectance UV-Vis spectra for Sn-Beta and SnO 2 -Beta.
- FIG. 34 depicts glucose isomerization conversion profiles at 383 K, using Sn-Beta as a catalyst. Reaction conditions were 10 wt % glucose (unlabeled or labeled) in water and 1:50 Sn:glucose molar ratio.
- FIG. 35 depicts molecular structures for an unlabeled glucose solution containing 35% glucose in the ⁇ -pyranose configuration (A) and 65% in the ⁇ -pyranose configuration (B). The same ratios are obtained for labeled glucose (glucose-D2), where 35% is in the ⁇ -pyranose configuration (C) and 65% is in the ⁇ -pyranose configuration (D).
- FIGS. 36-37 depict 13 C NMR spectra of unlabeled glucose, glucose-D2 before heating, and glucose-D2 after heating at 383 K without a catalyst.
- FIGS. 38-39 depict the results of reaction tests for the conversion of glucose to HMF using a biphasic system.
- the reaction conditions of the FIG. 38 series of experiments were 1:2 water to 1-butanol volume ratio, pH of 1 in HCl, and 35 g of NaCl in 100 g of water.
- FIG. 40 depicts the results of reaction tests for the conversion of glucose to HMF using a biphasic system.
- FIG. 41 depicts the results of reaction tests for the conversion of glucose to HMF using a biphasic system.
- FIG. 42 depicts the results of reaction tests for the conversion of glucose to HMF using a biphasic system.
- the reaction conditions were Sn-Beta to glucose molar ratio of 200, 1:3 water to organic phase volume ratio, pH of 1 in HCl, 35 g of NaCl in 100 g of water.
- FIGS. 43-45 depict the results of reaction tests for the conversion of glucose to HMF using a biphasic system.
- the reaction conditions were temp 160° C., Sn/Beta zeolite to glucose mole ratio of 1:200, pH of 1 in HCl, 1:2 water to 1-butanol volume ratio.
- FIGS. 43 and 44 provide reactivity data
- FIG. 45 provides X-ray diffraction (XRD) data before and after exposure to HCl at a pH of 1.
- XRD X-ray diffraction
- FIG. 46 depicts thermodynamic data of glucose to fructose isomerization based on data from Tewari, Y., Applied Biochemistry and Biotechnology 1990, 23, 187.
- FIG. 47 depicts an x-ray defraction pattern of Zn-CIT-6 synthesized according to the procedure described in Andy & Davis, Ind. Eng. Chem. Res. 2004, 43, 2922.
- FIG. 48 depicts a scanning electronic micrograph of the synthesized Zn-CIT-6, showing a crystal size of 0.5-0.6 microns.
- FIG. 49 depicts product distributions for the glucose isomerization reaction at 110° C. by using the CIT-6(SnCH 3 Cl 3 ) catalyst in the as prepared form (left) and calcined (right)
- conversion is defined as the moles of x reacted divided by the initial moles of x.
- Selectivity is defined as the moles of y produced divided by the moles of x reacted.
- Yield is defined as the moles of y produced divided by the initial moles of x.
- sugars are isomerized using chemical catalysis.
- chemical catalysis employing inexpensive inorganic materials to isomerize sugars may offer attractive advantages, including operation over a wider range of temperatures and longer lifetimes, faster reaction rates that could give shorter reactor residence times, and a higher resistance to impurities.
- glucose undergoes isomerization in the presence of base catalysts at temperatures ranging from 298 to 423 K; unfortunately, monosaccharides are unstable in alkaline media and readily degrade into numerous byproducts at temperatures above 313 K.
- base catalysts typically generate fructose yields ⁇ 10% (high-fructose selectivities [>90%] are only afforded at low glucose conversions [ ⁇ 10%]), thereby making them unlikely candidates for use in large-scale glucose processing.
- tin (Sn) or titanium (Ti) metal centers that can act as solid acids in aqueous media when incorporated in the framework of a siliceous material.
- tin (Sn) or titanium (Ti) metal centers that can act as solid acids in aqueous media when incorporated in the framework of a siliceous material.
- Ti titanium
- large-pore zeolites containing these types of acid centers are active in the isomerization of aldoses, such as glucose, while preventing sugar degradation reactions usually encountered in base-catalyzed processes.
- a monosaccharide is isomerized by, among other things, contacting the monosaccharide in aqueous medium with a catalyst.
- the catalyst may be, for example, an inorganic material containing metal centers.
- the inorganic material may be a siliceous material.
- the inorganic material may also be a porous material, or in particular a molecular sieve, or in particular a microporous material such as a zeolite.
- the inorganic material may be a high-silica zeolite.
- zeolites are aluminosilicates
- zeolites incorporating other constituents, for example zinc are known in the art, as are methods for synthesizing them.
- Some zeolites are termed high-silica, meaning that the ratio of silicon to aluminum in the framework is high, for example at least 10:1, or as high as 100:1 or even higher.
- High-silica zeolites may even be entirely free of aluminum. The higher the ratio of silicon to aluminum, the more neutral and hydrophobic the framework of the zeolite becomes.
- the pores of the material may be designed such that the pores are sufficiently large to admit monosaccharide or other reactants or products to the interior of the porous material.
- the inorganic material is a zeolite
- a particular zeolite with a desired pore size may be selected. Pore size is one way to classify zeolites, and zeolites of a variety of pore sizes are known in the art.
- the pore size of the zeolite may also be selected to exclude undesirable or interfering molecules.
- the inorganic material is a porous material
- the material may be designed such that the catalyst reactivity is afforded inside the material, whereby the reactants enter the material through the pores, react to form products, and then the products leave the material through the pores.
- surface reactivity may be present, but it may also be insubstantial, negligible, or entirely absent.
- the inorganic material may contribute to the catalytic activity, but in others, the metal centers provide the catalytic activity.
- the metal centers are incorporated into the framework of the inorganic material.
- zeolites may contain metals within the framework of the zeolite. Examples of such zeolites are known in the art. E.g., Corma A. et al. (2001) Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-Villiger oxidations, Nature 412(6845):423-25. Notwithstanding this knowledge, successful incorporation of metals into the framework of a zeolite generally should be proven by characterization of the zeolite.
- the metal centers act as Lewis acids.
- the metal may lend Lewis acid activity to the inorganic material.
- a number of metals are known generally in the prior art to act as Lewis acids, depending upon whether they are present as cations, complexes, or covalent compounds, for example aluminum, boron, chromium, cobalt, iron, titanium, tin, and others.
- the metal centers are tin or titanium.
- Other metals known in the art to have Lewis acid activity are also contemplated for incorporation into the catalyst.
- the catalyst may be a zeolite containing tin or titanium incorporated into the framework of the zeolite.
- the catalyst may be a high-silica zeolite containing tin or titanium incorporated into the framework of the zeolite.
- the catalyst includes zeolite beta.
- zeolite beta is a zeolite defined by the topology *BEA, the characteristics of which are set forth, for example, in the Atlas of Zeolite Framework Types, Sixth Edition (Baerlocher et al., 2007).
- Other zeolites known in the art are contemplated.
- the choice of zeolite depends upon the appropriate framework size, shape, and constituents, depending upon the reaction to be catalyzed, reactants, and products.
- zeolite beta a zeolite with pore sizes capable of admitting glucose and fructose is desirable, for example, zeolite beta. Larger reactants and products would call for materials with proportionately larger pores.
- the catalyst includes zeolites such as TS-1, which is a titanosilicate material with the MFI topology.
- zeolites such as TS-1, which is a titanosilicate material with the MFI topology.
- Various other large pore and extra-large pore zeolites are contemplated as well, for example CIT-1, ZSM-12, SSZ-33, SSZ-26, CIT-5, or high silica FAU.
- the porous material is an ordered mesoporous silica material.
- a monosaccharide is isomerized by, among other things, contacting the monosaccharide in aqueous medium with an ordered mesoporous silica material containing tin or titanium, incorporated into the framework of the material.
- the mesoporous silica material may be, for example, MCM-41, SBA-15, TUD-1, HMM-33 or FSM-16.
- the catalyst is contacted with the monosaccharide in aqueous solution, meaning a solution where the solvent is water.
- aqueous solution meaning a solution where the solvent is water.
- the catalysts disclosed herein may be contacted with monosaccharide in other solvents, for example alcohols, although as disclosed elsewhere herein, the choice of solvent significantly impacts the outcome of the chemical reaction.
- the catalyst is contacted with a carbohydrate.
- the catalyst may be contacted with a monosaccharide, disaccharide, trisaccharide, oligosaccharide or polysaccharide.
- any combination of carbohydrates may be contacted with the catalyst as appropriate.
- carbohydrates of any chirality may be contacted with the catalyst.
- the monosaccharide may be an aldose, such as an aldotriose, aldotetrose, aldopentose or aldohexose.
- the aldoses may include glyceraldehyde, erthrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose or talose.
- the monosaccharide may be a ketose, such as a ketotriose, ketotetrose, ketopentose, or ketohexose.
- the ketoses may include dihydroxyacetone, erythrulose, ribulose, xylulose, psicose, fructose, sorbose, or tagatose.
- the disaccharide may be any combination of monosaccharides, for example sucrose, lactulose, lactose, maltose, trehalose, cellobiose, kojibiose, nigerose, isomaltose, sophorose, laminarbiose, gentiobiose, turanose, maltulose, palatinose, gentiobiulose, mannobiose, melibiose, melibulose, rutinose, rutinulose or xylobiose.
- monosaccharides for example sucrose, lactulose, lactose, maltose, trehalose, cellobiose, kojibiose, nigerose, isomaltose, sophorose, laminarbiose, gentiobiose, turanose, maltulose, palatinose, gentiobiulose, mannobiose, melibiose,
- Mixtures of carbohydrates may also be contacted with the catalysts disclosed herein, including mixtures of carbohydrates that are the byproduct of hydrolysis reactions of biomass materials such as starch and cellulose, for example maltose and cellobiose.
- oligosaccharides and polysaccharides may be contacted with the catalysts disclosed herein, for example fructo-oligosaccharides and galacto-oligosaccharides, as well as starches, celluloses, and chitins.
- the aqueous medium includes between about 0.001 weight percent monosaccharide and the maximum solubility of the monosaccharide in the medium at a selected temperature.
- the aqueous medium may include between about 0.001 weight percent monosaccharide and about 50 weight percent monosaccharide, or between about 10 weight percent monosaccharide and about 50 weight percent monosaccharide.
- the aqueous medium may also include between about 25 weight percent monosaccharide and about 50 weight percent monosaccharide. Higher concentrations are industrially desirable because of the increased utilization of processing equipment, among other reasons. The particular monosaccharide concentration selected depends in part on the solubility of the monosaccharide selected.
- the isomerization reaction substantially reaches thermodynamic equilibrium.
- the equilibrium conversions are depicted in FIG. 46 .
- the isomerization reaction is performed by a chemical catalyst that provides substantially the same conversion and selectivity as prior art enzymatic systems.
- the pH of the aqueous medium is acidic, meaning less than 7.0.
- monosaccharides may be isomerized in non-acidic conditions, for example as disclosed herein
- isomerization in acid conditions also disclosed herein, has notable utility. Indeed, the ability to isomerize sugars in an acidic solution is essential to overcome some of the main bottlenecks encountered during base catalysis, some of which include the neutralization of active sites by acidic byproducts and the low stability of sugars in alkaline environments. Furthermore, working at low pH values affords opportunities to couple upstream and downstream acid-catalyzed reactions, e.g., hydrolysis or dehydration, with the glucose isomerization reaction without the need to use additional unit operations.
- the starch hydrolysis step (typically performed in a separate set of reactors using either acid catalysts or a combination of enzymes) required prior to the isomerization step could be combined with the glucose isomerization step.
- the base-catalyzed isomerization step required to convert glucose into fructose before performing the acid-catalyzed dehydration step could be combined in a single reactor to obtain higher product yields more efficiently.
- the pH of the aqueous medium is between about 0 and about 4. In further methods disclosed herein, the pH of the aqueous medium is between about 0 and about 2. A pH of between about 0 and about 2, including 2, is particularly useful for coupling isomerization with the hydrolysis of starch and/or the dehydration of fructose to form HMF.
- the aqueous medium comprises a salt.
- Salt may be present for a number of reasons, for example, it may be carried over from a previous process, and salt tolerance may be advantageous for economic and efficiency reasons.
- salt may also be added intentionally in order to facilitate partitioning across multiple liquid phases.
- the salt may include a cation which could be any metal, for example sodium, potassium, magnesium, calcium, lithium or others.
- the salt may likewise include an anion such as acetate, alkylphosphate, alkylsulfate, carbonate, chromate, citrate, cyanide, formate, glycolate, halide, hexafluorophosphate, nitrate, nitrite, oxide, phosphate, sulfate, tetrafluoroborate, tosylate, triflate or bis-trifluorsulfonimide.
- the salt may be sodium chloride, potassium chloride, magnesium chloride, or potassium bromide.
- the isomerization is carried out at a temperature of between about 50° C. and about 250° C.
- the choice of temperature influences reaction kinetics as well as conversion and selectivity.
- the maximum temperature for the reaction may depend upon whether the reactor is pressurized, and if so, to what pressure.
- the isomerization may be carried out at a temperature of between about 90° C. and about 180° C.
- the isomerization may be carried out at a temperature of between about 90° C. and about 140° C. Where feasible, lower temperatures may be desirable to conserve energy.
- the isomerization may be carried out for less than about 90 minutes.
- a reaction must be allowed to proceed long enough to reach a desired conversion. Shorter reaction times may be desirable from an industrial point of view for efficiency reasons.
- the isomerization may be carried out for less than about 60 minutes, or less than about 30 minutes. Another reason to use shorter reaction times is the potential for the buildup of undesirable degradation products.
- the conditions of the monosaccharide isomerization reaction are selected such that a zeolite catalyst may be used batchwise for at least three reaction cycles without significant reduction in performance and without the need for calcination.
- a stable catalyst offers several advantages of industrial importance, including increased efficiency, reduced cost, and reliability.
- a Sn-Beta catalyst is stable and maintains its activity both after reuse and after calcination. For example, successive cycles of glucose isomerization were performed with no intermediate treatment of the catalyst, and conversion and selectivity were maintained.
- a step of calcining in air in between cycles restores performance. Whether the catalyst suffers decreased performance may depend, in part, upon the choice of catalyst and the choice of reaction conditions. For example, where the reaction time and temperature are kept to modest levels, for example 383K and 30 minutes, no intermediate step of calcining is necessary.
- the product of the monosaccharide isomerization is then dehydrated.
- the dehydration may be conducted to form furan derivatives useful as chemical intermediates.
- glucose is converted to 5-hydroxymethylfurfural (HMF) by, among other things, contacting glucose in aqueous medium with a high silica zeolite containing tin or titanium, incorporated into the framework of the zeolite, the zeolite having pores capable of admitting the glucose, to provide fructose and then dehydrating the fructose.
- HMF 5-hydroxymethylfurfural
- the catalyst includes zeolites such as Beta.
- zeolites such as Beta.
- Various other large pore and extra-large pore zeolites are contemplated as well, for example CIT-1, ZSM-12, SSZ-33, SSZ-26, CIT-5, or high silica FAU.
- the porous material is an ordered mesoporous silica material.
- a monosaccharide is isomerized by, among other things, contacting the monosaccharide in aqueous medium with an ordered mesoporous silica material containing tin or titanium, incorporated into the framework of the material.
- the mesoporous silica material may be, for example, MCM-41, SBA-15, TUD-1, HMM-33 or FSM-16.
- the product of the monosaccharide isomerization may be maintained in the aqueous medium while it is dehydrated.
- fructose may be maintained in the aqueous medium while it was dehydrated.
- the dehydration of saccharides to form furan derivatives is well studied, and in particular the dehydration of fructose to form HMF is known in the art.
- the dehydration of the product of the isomerization reaction is carried out in the presence of an acid catalyst.
- the catalyst may be an inorganic acid dissolved in the aqueous medium, such as HCl.
- the catalyst may also be, for example, a solid acid catalyst such as a protonated high silica zeolite having a *BEA topology.
- acid sources may be useful as well, such as cation exchange resins, lewis acids, silica-alumina materials, titania-alumina materials, mineral acids, heteropolyacids, nitric acid, sulfuric acid, phosphoric acid, boric acid, oxalic acid, levulinic acid, citric acid, niobium oxide, vanadium phosphate or niobium phosphate.
- cation exchange resins such as cation exchange resins, lewis acids, silica-alumina materials, titania-alumina materials, mineral acids, heteropolyacids, nitric acid, sulfuric acid, phosphoric acid, boric acid, oxalic acid, levulinic acid, citric acid, niobium oxide, vanadium phosphate or niobium phosphate.
- the isomerization and dehydration reactions may be carried out in sequence or simultaneously, or some combination of the two.
- a monosaccharide is contacted with an isomerization catalyst and a dehydration catalyst in aqueous solution, both reactions can proceed together.
- glucose is contacted with an isomerization catalyst in an acidic aqueous solution, the glucose reacts first to form fructose and then to form HMF.
- the particular reactions conditions may be, among others, any of the conditions disclosed in connection with isomerization.
- the pH of the aqueous medium is between about 0 and about 4. In further methods disclosed herein, the pH of the aqueous medium is between about 0 and about 2. In still other methods combining isomerization and dehydration disclosed herein, the aqueous medium comprises a salt, for example including a cation which could be any metal, for example sodium, potassium, magnesium, calcium, lithium or others.
- the salt may likewise include an anion such as acetate, alkylphosphate, alkylsulfate, carbonate, chromate, citrate, cyanide, formate, glycolate, halide, hexafluorophosphate, nitrate, nitrite, oxide, phosphate, sulfate, tetrafluoroborate, tosylate, triflate or bis-trifluorsulfonimide.
- the salt may be sodium chloride, potassium chloride, magnesium chloride, or potassium bromide.
- the isomerization is carried out at a temperature of between about 50° C. and about 250° C.
- the choice of temperature influences reaction kinetics as well as conversion and selectivity.
- the maximum temperature for the reaction may depend upon whether the reactor is pressurized, and if so, to what pressure.
- the isomerization may be carried out at a temperature of between about 90° C. and about 180° C.
- the isomerization may be carried out at a temperature of between about 90° C. and about 140° C. Where feasible, lower temperatures may be desirable to conserve energy.
- the isomerization may be carried out for less than about 90 minutes.
- a reaction must be allowed to proceed long enough to reach a desired conversion. Shorter reaction times may be desirable from an industrial point of view for efficiency reasons.
- the isomerization may be carried out for less than about 60 minutes, or less than about 30 minutes. Another reason to use shorter reaction times is the potential for the buildup of undesirable degradation products.
- the combination isomerization-dehydration reaction can be conducted in a biphasic system, for example as described in U.S. Pat. No. 7,572,925.
- a biphasic system involves two substantially immiscible liquid phases, one aqueous and one organic.
- a biphasic system in principle offers advantages for conversion, selectivity, and purification efficiency.
- the isomerization of the saccharide takes place in the aqueous phase, as does the dehydration of the isomerization product.
- both the isomerization of glucose into the fructose and the dehydration of fructose into HMF take place in the aqueous phase.
- the catalysts for each of those reactions is provided in the aqueous phase.
- the dehydration product for example HMF
- HMF is then extracted into the organic layer.
- the aqueous medium may be contacted with an organic medium capable of extracting HMF from the aqueous medium, wherein the organic medium is substantially immiscible with the aqueous medium.
- the HMF is produced in the aqueous medium, and extracted from the aqueous medium to the organic medium as it is produced.
- the organic medium includes 1-butanol or THF.
- Some components of the organic layer may include compounds that are somewhat miscible with water.
- Other organic media components disclosed include, for example, DMSO, DMF, N-methylpyrrolidinone, acetonitrile, acetone, butanone, pentanone, hexanone, heptanone, and the like.
- starch may be hydrolyzed by acid to form glucose.
- isomerization of glucose using catalysts disclosed herein performs well in acidic conditions.
- methods are disclosed herein for converting starch to 5-hydroxymethylfurfural by, among other things, hydrolyzing the starch in acid to provide glucose in an acidic aqueous medium, contacting glucose in aqueous medium with a high silica zeolite containing tin or titanium, incorporated into the framework of the zeolite, the zeolite having pores capable of admitting the glucose, to provide fructose, and dehydrating the fructose.
- the conversion of starch to HMF can be effected in a biphasic system, for example in accordance with U.S. Pat. No. 7,572,925.
- All of the variations and disclosure applicable to the isomerization reaction and to the combination of the isomerization and dehydration reactions, whether in aqueous solution or in a biphasic system, are applicable to the starch to HMF system.
- the acidic aqueous medium is contacted with an organic medium capable of extracting 5-hydroxymethylfurfural from the acidic aqueous medium, wherein the organic medium is substantially immiscible with the aqueous medium.
- 5-hydroxymethylfurfural is produced in the acidic aqueous medium, and extracted from the aqueous medium to the organic medium as it is produced.
- Ti-Beta zeolite was prepared as follows: 7.503 g of tetraethylammonium hydroxide solution (Sigma-Aldrich, 35% wt in water) were diluted with 15 g of water. Then, 7.016 g of tetraethylorthosilicate (Sigma-Aldrich, 98% wt) and 0.201 g of titanium (IV) isopropoxide (Sigma-Aldrich, 97% wt) were added to the solution. The mixture was stirred until complete hydrolysis of the tetraethylorthosilicate and titanium (IV) isopropoxide, allowing evaporation of ethanol, isopropanol and required water until desired water ratio. Finally, 0.670 g of HF solution (Mallinckrodt, 52% wt in water) were added resulting in a thick gel.
- HF solution Merallinckrodt, 52% wt in water
- the gel composition was SiO 2 /0.021 TiO 2 /0.54 TEAOH/0.53 HF/6.6 H 2 O. This gel was transferred to a Teflon-lined stainless steel autoclave and heated at 140° C. for 14 days. The solids were recovered by filtration, extensively washed with water, and dried at 100° C. overnight. The solid material shows the Beta zeolite topology (see Ti-Beta XRD pattern in FIG. 13 ). The solid is calcined at 580° C. for 6 hours to remove the organic content located into the crystalline material.
- UV-vis diffuse reflectance spectrum of the calcined sample shows the presence of a unique band at ⁇ 200-250 nm, which can be assigned to Ti tetrahedrally coordinated into the zeolite framework (see Ti-Beta in FIG. 12 ).
- Sn-Beta zeolite was prepared as follows: 7.57 g of tetraethylammonium hydroxide solution (Sigma-Aldrich, 35 wt % in water) was diluted with 15 g of water. Next, 7.011 g of tetraethylorthosilicate (Sigma-Aldrich, 98 wt %) and 0.121 g of tin (IV) chloride pentahydrate (Sigma-Aldrich, 98 wt %) were added to the solution. The mixture was stirred until complete hydrolysis of the tetraethylorthosilicate was obtained, and then allowed to reach the desired water ratio by complete evaporation of ethanol and some water. Finally, 0.690 g of HF solution (Mallinckrodt, 52 wt % in water) was added resulting in a thick gel.
- HF solution Merallinckrodt, 52 wt % in water
- the gel composition was SiO 2 /0.01 SnCl 4 /0.55 TEAOH/0.54 HF/7.52 H 2 O. This gel was transferred to a Teflon-lined stainless steel autoclave and heated at 140° C. for 50 days. The solids were recovered by filtration, extensively washed with water, and dried at 100° C. overnight. The solid was calcined at 580° C. for 6 hours to remove the organic content located into the crystalline material. X-ray diffraction confirmed that the solid material has the Beta zeolite topology (see Sn-Beta XRD pattern in FIG. 13 ).
- UV-vis diffuse reflectance spectrum of the calcined sample shows the presence of a unique band at ⁇ 200-250 nm, which can be assigned to Sn tetrahedrally coordinated into the zeolite framework (see Sn-Beta in FIG. 12 ).
- Scanning electron microscopy (SEM) shows the Sn-Beta crystals are several microns in size, FIGS. 6-7 , and energy dispersive X-ray spectroscopy (EDS) measurements for the Sn-Beta sample show an atomic ratio Si:Sn of 96:1.
- TS-1 was synthesized following the method reported in the patent literature (U.S. Pat. No. 4,410,501).
- TS-1 was crystallized from a clear solution prepared by mixing titanium butoxide (TNBT, Sigma-Aldrich), tetraethylorthosilicate (TEOS, Sigma-Aldrich), tetrapropylammonium hydroxide (TPAOH, 1M, Sigma-Aldrich) and distilled water. The mixture was stirred until complete hydrolysis of the tetraethylorthosilicate and titanium butoxide was obtained, then allowing complete evaporation of ethanol, butanol and some water until the desired water ratio was reached.
- TBT titanium butoxide
- TEOS tetraethylorthosilicate
- TPAOH tetrapropylammonium hydroxide
- the gel composition was SiO 2 /0.03 TiO 2 /0.44 TPAOH/30 H 2 O.
- the TS-1 reaction mixture was charged into Teflon-lined autoclaves and allowed to crystallize at 175° C. for 5 days. The autoclave was rotated at 50 RPM. After cooling, the solid was recovered by filtration, extensively washed with water, and dried at 100° C. overnight. The material was calcined at 580° C. for 6 hours to remove the organic content located within the crystalline material.
- the Ti-MCM-41 sample was synthesized as follows: a solution of hexadecyltrimethylammonium bromide (C16TABr) was prepared (1.93 g of C16TABr in 15.1 g of water). Then, 6.42 g of tetramethylammonium hydroxide solution (25%, Aldrich) was added. After homogenization, 7.015 g of tetraethylorthosilicate (Sigma-Aldrich, 98% wt) and 0.19 g of titanium (IV) isopropoxide (Sigma-Aldrich, 97% wt) were added to the solution.
- the mixture was stirred until complete hydrolysis of the tetraethylorthosilicate and titanium (IV) isopropoxide was obtained.
- complete evaporation of ethanol, isopropanol and some water was allowed until the desired water ratio was reached.
- the final composition was: 1.0 SiO2/0.02 TiO 2 /0.16 C 16 TABr/0.26 TMAOH/24.8 H 2 O.
- the homogeneous gel was sealed in Teflon-lined stainless steel autoclaves and heated at 135° C. under static conditions during 48 hours. The solid was recovered by filtration, extensively washed with water, and dried at 100° C. overnight. The solid was calcined at 580° C. for 6 hours to remove the organic content located within the ordered material.
- the Sn-MCM-41 sample was synthesized as follows: a solution of hexadecyltrimethylammonium bromide (C16TABr) was prepared (1.46 g of C16TABr in 4.3 g of water). Then, 6.34 g of tetramethylammonium hydroxide solution (25%, Aldrich) was added. After homogenization, 0.088 g SnCl 4 .5H 2 O (98%, Aldrich) and 3.76 g of colloidal silica solution (Ludox AS-40, Sigma-Aldrich) were added with continuous stirring.
- C16TABr hexadecyltrimethylammonium bromide
- the final composition was: 1.0 SiO 2 /0.01 SnCl4/0.16 C 16 TABr/0.35 TMAOH/25 H 2 O.
- the homogeneous gel was sealed in Teflon-lined stainless steel autoclaves and heated at 135° C. under static conditions during 48 hours.
- the solid was recovered by filtration, extensively washed with water, and dried at 100° C. overnight.
- the solid was calcined at 580° C. for 6 hours to remove the organic content located within the ordered material.
- Powder X-ray diffraction (XRD) patterns were collected by using a Scintag XDS 2000 diffractometer using Cu Ka radiation.
- Scanning electron microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS) measurements were recorded on a LEO 1550 VP FE SEM at an electron high tension (EHT) of 10 kV.
- UVVis measurements were recorded using a Cary 3G spectrophotometer equipped with a diffuse reflectance cell.
- Glucose isomerization experiments were carried out in 10 ml thick-walled glass reactors (VWR) heated in a temperature-controlled oil bath placed on top of an digital stirring hotplate (Fisher Scientific).
- VWR thick-walled glass reactors
- Fether Scientific digital stirring hotplate
- 1.5 g of an aqueous solution composed of 10 wt % glucose and the corresponding catalyst amount to achieve a 1:50 metal:glucose molar ratio (typically ⁇ 70 mg) were added to the reactor and sealed.
- the reactor was placed in the oil bath and removed at specific times. The reaction was stopped by cooling the reactor in an ice bath, and small aliquots were taken for analysis.
- the Ti-Beta catalyst while active, was not as effective in these conditions as the Sn-Beta catalyst, generating after 45 min at 110° C., a fructose selectivity of 80% at 18% glucose conversion, and after 45 min at 140° C. a fructose selectivity of 68% at a 44% glucose conversion.
- the following table summarizes glucose isomerization experiments using various catalysts in water. Reactions were performed with a 10 wt % glucose solution, using the corresponding amount of catalyst to maintain a 1:50 metal:glucose molar ratio, with the exception of entry 10, indicated by *, which reports the results of a reaction of a 45 wt % glucose solution, using a 225:1 glucose:Sn molar ratio.
- the ** indicates that an unidentified sugar, rather than mannose, was obtained with Ti-Beta.
- the reported 5 wt % yield was calculated using the response factor associated with hexoses.
- silica materials containing either Sn or Ti metal centers were screened for their activity in the glucose isomerization reaction. Specifically, Sn and Ti metal centers were incorporated into the framework of a large-pore zeolite (Beta), Ti was incorporated into a medium-pore zeolite (TS-1), and Sn and Ti were incorporated into an ordered mesoporous silica (MCM-41). Under these conditions, Sn-Beta and Ti-Beta showed the highest glucose isomerization activity, reaching glucose conversions above 50% in 90 min at 413 K ( FIG. 24 ). In contrast, Sn-MCM41 and Ti-MCM41 only revealed moderate activity, and TS-1 was virtually inactive under the same reaction conditions ( FIG. 24 ).
- Reactivity differences between TS-1 and Ti-Beta indicate that glucose molecules are able to diffuse into the pores of the Beta zeolite (ca. 0.8 nm pore diameter), but not into the pores of TS-1 (0.5-0.6 nm pore diameter).
- Sn-Beta catalyst isomerizes glucose with superior performance when compared to Ti-Beta.
- a 10 wt % glucose solution containing a catalytic amount of Sn-Beta (1:50 Sn:glucose molar ratio) generated product yields of approximately 46% (w/w) glucose, 31% (w/w) fructose, and 9% (w/w) mannose after 30 min and 12 min at 383 K and 413 K, respectively.
- the Ti-Beta catalyst achieved much lower glucose conversions, even when the reaction was allowed to proceed for longer periods of time (entries 4 and 7).
- the onset of auto-catalyzed degradation reactions decreased total saccharide yields with increased reaction times ( FIGS. 25-30 ). Varying the reaction temperature did not appear to have an impact on the total amount of sugar lost at a given glucose conversion value, thus suggesting that the degradation reaction pathway has an apparent activation barrier similar to that of the isomerization reaction.
- the Sn-Beta catalyst can be used with more concentrated glucose solutions like those employed in large-scale conversion.
- a product distribution of 46% (w/w) glucose, 29% (w/w) fructose, and 8% (w/w) mannose was obtained after reacting a 45 wt % glucose solution containing a catalytic amount of Sn-Beta (1:225 Sn:glucose molar ratio) for 60 min at 383 K (entries 4 and 10).
- This result approximates those obtained in the industrial enzymatic process, and is a high fructose yield obtained from a highly concentrated glucose solution using an inorganic catalyst.
- Glucose deuterated at the C-2 position was used to perform NMR studies on the isomerization reaction.
- the proton at the C-2 position plays a fundamental role in the reaction mechanism regardless of which pathway is followed.
- 13 C NMR spectra of glucose-D2 heated in water at the reaction temperature (383K) in the absence of catalyst reveal that no isotopic scrambling occurs ( FIGS. 36-37 ). This result is important because it demonstrates the inertness of the C-D bond in water at reaction conditions and indicates that any isotopic rearrangement within the molecule during the reaction is entirely due to the actions of the catalyst.
- the basic catalyst operates by a proton-transfer mechanism whereby the deuterium atom is removed from the a-carbonyl carbon of glucose-D2 to form the corresponding enolate, and a proton from solution is subsequently re-incorporated into the molecule, yielding some unlabeled glucose along with the unlabeled fructose ( FIG. 18 A).
- Sn-Beta synthesized by a procedure known to fully incorporate tin into the framework (SnCl, as the tin source) is highly active for the isomerization reaction, whereas Sn-Beta synthesized using SnO, as the tin source is completely inactive ( FIG. 33A ).
- the diffuse reflectance UV-Vis spectrum for the active material shows a single band centered at 220 nm, assigned to tetrahedrally coordinated metal, while the spectrum for the non-active material shows a band centered at 300 nm, assigned to octahedrally coordinated metal in extra-framework positions ( FIG. 33B ).
- Glucose HMF Temp Time Conversion Selectivity Entry System Catalyst ° C. (min) % % 1 Single Sn-Beta, 160 90 65 6 phase in HCl H 2 O 2 Biphasic: Sn-Beta, 160 90 5 25 H 2 O/1- HCl butanol 3 Biphasic: Sn-Beta, 160 90 7 53 H 2 O/1- HCl butanol/NaCl 4 Biphasic: Sn-Beta 160 90 9 16 H 2 O/1- butanol/NaCl 5 Biphasic: Sn-Beta, 180 70 4 51 H 2 O/1- HCl butanol/NaCl 6 Biphasic: Sn-Beta, 180 70 84 70 H 2 O/THF HCl
- Zeolite Sn-CIT-6 was synthesized for the glucose isomerization reaction.
- the synthesis of the zincosilicate CIT-6 was done following the procedure described in the literature (Andy & Davis, Ind. Eng. Chem. Res. 2004, 43, 2922).
- the x-ray diffraction pattern of the as-synthesized material is depicted in FIG. 47 .
- An electron micrograph of the as-synthesized material is depicted in FIG. 48 .
- CIT-6 was recovered by filtration washing the solid with water, and dried overnight at 100° C. Next, the sample was heated to 130° C. for 2 h with vacuum to eliminate the adsorbed water.
- the grafting of Sn (in the form of SnCl 3 CH 3 ) in the CIT-6 was carried out with a solution of the corresponding amount of grafting agent (Si/Sn ⁇ 100-125) in anhydrous chloroform at room temperature. After 1 h, triethylamine was added in the mixture to trap the hydrochloric acid formed in the grafting process. The suspension was maintained stirred during 2 days. The sample was washed with chloroform and dried at 100° C. overnight. The final ratio of Si/Sn was 110 for CIT-6(SnCH 3 Cl 3 ) (calculated by EDS). A portion amount of the sample was calcined at 580° C. for 6 hours.
- the reaction conditions for the glucose isomerization were: 10% wt of glucose in water with a sugar:Sn ratio of 100 at 110° C. after 90 minutes.
- the catalyst was active for the glucose isomerization reaction. This suggests that for an effective grafting, the alkyl groups should be removed oxidatively by calcination. This trend was also observed and described by Corma et al., J. Catal, 2003, 219, 242.
- FIG. 49 depicts product distributions for the glucose isomerization reaction at 110° C. by using the CIT-6(SnCH 3 Cl 3 ) catalyst in the as prepared form (left) and calcined (right).
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US11192872B2 (en) | 2017-07-12 | 2021-12-07 | Stora Enso Oyj | Purified 2,5-furandicarboxylic acid pathway products |
US12049456B2 (en) | 2021-11-30 | 2024-07-30 | Stora Enso Oyj | Purified 2,5-furandicarboxylic acid pathway products |
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FR2979345B1 (fr) * | 2011-08-26 | 2014-02-21 | Centre Nat Rech Scient | Procede d'isomerisation du glucose en fructose |
DE102012200086A1 (de) * | 2011-09-30 | 2013-04-04 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung von Furanverbindungen aus nachwachsenden Rohstoffen |
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US9108190B1 (en) | 2012-09-12 | 2015-08-18 | University Of Massachusetts | Rapid synthesis of beta zeolites |
US8772515B2 (en) * | 2012-10-11 | 2014-07-08 | Wisconsin Alumni Research Foundation | Method to convert biomass to 5-(hydroxymethyl)-furfural (HMF) and furfural using lactones, furans, and pyrans as solvents |
CN103113329B (zh) * | 2013-02-19 | 2015-04-08 | 齐齐哈尔大学 | 一种由固体超强酸催化制备五羟甲基糠醛的方法 |
WO2014154676A1 (de) * | 2013-03-27 | 2014-10-02 | Annikki Gmbh | Verfahren zur isomerisierung von glucose |
US9255120B2 (en) | 2013-04-11 | 2016-02-09 | California Institute Of Technology | Conversion of glucose to sorbose |
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CN106492874A (zh) * | 2016-09-06 | 2017-03-15 | 安徽理工大学 | 一种制备5‑羟甲基糠醛高效催化剂的配方及应用条件 |
WO2018148939A1 (zh) * | 2017-02-17 | 2018-08-23 | 中国科学院宁波材料技术与工程研究所 | 一种单糖差向异构化反应催化剂 |
CN112746136B (zh) * | 2019-10-31 | 2022-03-08 | 中国石油化工股份有限公司 | 一种果糖的化学制备方法 |
CN113372308B (zh) * | 2021-05-10 | 2022-06-10 | 浙江糖能科技有限公司 | 一种双-(5-甲酰基糠基)醚的制备方法 |
EP4299566A1 (fr) * | 2022-07-01 | 2024-01-03 | IFP Energies nouvelles | Procede de production de 5-hydroxymethylfurfural |
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